Metal complex carrying a 2-phospa-tricyclo[3.3.1.1(3.7)]decyl radical as a ligand in hydroformylation

ABSTRACT

In a process for the hydroformylation of ethylenically unsaturated compounds, at least one ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen in the presence of a ligand-metal complex of ruthenium, rhodium, palladium, iridium and/or platinum, where the ligand-metal complex comprises a monophosphine, monophosphinite or monophosphinamidite ligand of the formula I                    
     where 
     A together with the phosphorus atom to which it is bound forms a 2-phosphatricyclo[3.3.1.1{3,7}]decyl radical in which one or more nonadjacent carbon atoms may be replaced by heteroatoms and which may be substituted, and 
     R′ is hydrogen or an organic radical having a molecular weight of up to 20 000 bound via a carbon atom or oxygen atom or nitrogen atom. 
     The process is particularly useful for the hydroformylation of internal branched olefins and lower pressures and/or temperatures are required in the hydroformylation than when using other phosphorus ligands.

This application is a 371 of PCT/EP01/05404 filed May 11, 2001.

The present invention relates to a process for the hydroformylation ofethylenically unsaturated compounds, in which at least one ethylenicallyunsaturated compound is reacted with carbon monoxide and hydrogen in thepresence of a ligand-metal complex of ruthenium, rhodium, palladium,iridium and/or platinum, and to a ligand-metal complex suitable for theprocess.

Hydroformylation or the oxo process is an important industrial processand is used for preparing aldehydes by reaction of ethylenicallyunsaturated compounds with carbon monoxide and hydrogen. The reactionitself is strongly exothermic and generally proceeds undersuperatmospheric pressure and elevated temperatures in the presence ofcatalysts. In industrial practice, cobalt catalysts were first employed,but rhodium catalysts now predominate. To stabilize therhodium-containing catalyst during the reaction and to avoiddecomposition of the catalyst with precipitation of metallic rhodiumduring the work-up, phosphorus-containing ligands are generally used ascocatalysts. In the case of lower α-olefins, the use oftriphenylphosphine and other triarylphosphines, in particular, ascocatalysts has proven useful (cf., for example, J. Falbe, New Synthesiswith Carbonmonoxide, Springer, Berlin, 1980, p. 55ff). Although lowerα-olefins can be hydroformylated very well usingtriarylphosphine-modified rhodium catalysts, this catalyst system is notvery suitable for internal and internal branched olefins and for higherα-olefins. Thus, internal and internal branched double bonds arehydroformylated only very slowly in the presence of such a catalyst. Forthis reason, the hydroformylation of substrates having internal and/orinternal branched double bonds requires use of high pressures and/ortemperatures.

WO 98/42717 describes carbonylation reactions in the presence ofdiphosphines in which at least one phosphorus atom is part of a2-phosphatricyclo[3.3.1.1{3,7}]decyl group.

FR 118524 describes, inter alia, the hydroformylation of olefiniccompounds in the presence of a cobalt carbonyl catalyst and a cocatalystin the form of a trioxaphosphaadamantane.

It is an object of the present invention to provide a process for thehydroformylation of ethylenically unsaturated compounds in the presenceof a ligand-metal complex of ruthenium, rhodium, palladium, iridiumand/or platinum as catalyst, by means of which ethylenically unsaturatedcompounds, in particular ethylenically unsaturated compounds havinginternal and/or internal branched double bonds can be reacted underpressure and/or temperature conditions which are as mild as possible.

We have found that this object is achieved by a process for thehydroformylation of ethylenically unsaturated compounds, in which atleast one ethylenically unsaturated compound is reacted with carbonmonoxide and hydrogen in the presence of a ligand-metal complex ofruthenium, rhodium, palladium, iridium and/or platinum, where theligand-metal complex comprises a monophosphine, monophosphinite ormonophosphinamidite ligand of the formula I

where

A together with the phosphorus atom to which it is bound forms a2-phosphatricyclo[3.3.1.1{3,7}]decyl radical in which one or morenonadjacent carbon atoms may be replaced by heteroatoms and which may besubstituted, and

R′ is hydrogen or an organic radical having a molecular weight of up to20 000 bound via a carbon atom or oxygen atom or nitrogen atom.

In addition, the invention provides a metal-ligand complex comprising ametal selected from among ruthenium, rhodium, palladium, iridium and/orplatinum and at least one monophosphine or monophosphinite ligand asdefined above.

It has been found that ethylenically unsaturated compounds, inparticular those having internal branched double bonds, can be reactedby means of the process of the present invention at significantly lowertemperatures and/or pressures than those required for thehydroformylation of the same substrates using the same catalyticallyactive metal but other phosphorus-containing cocatalysts, e.g.triarylphosphines. In particular, the process of the present inventionmakes it possible to hydroformylate ethylenically unsaturated compounds,in particular those having internal branched double bonds, at pressuresof less than 100 bar, preferably less than 80 bar.

Tricyclo[3.3.1.1{3,7}]decane is also known under the trivial name“adamantane”. In the 2-phosphatricyclo[3.3.1.1{3,7}]decyl radical of theligand used according to the present invention, one or more nonadjacentcarbon atoms, which are preferably not adjacent to the phosphorus atom,may be replaced by heteroatoms, preferably oxygen atoms and/or nitrogenatoms. Preference is given to the carbon atoms in the positions 6, 9 and10 being replaced by heteroatoms, in particular oxygen atoms.

The 2-phosphatricyclo[3.3.1.1{3,7}]decyl radical may be substituted by,for example, from 1 to 8, preferably from 1 to 4, substituents. Inparticular, it may bear substituents on one or more of its carbon atoms.Preference is given to one or more carbon atoms in the positions 1, 3, 5and/or 7, in particular all carbon atoms in positions 1, 3, 5 and 7,bearing substituents which are preferably identical. Suitablesubstituents are, for example, halogen, alkyl, cycloalkyl, haloalkyl,aryl and or aralkyl. The carbon atoms in the positions 4 and/or 8 maybear one or two substituents, e.g. C₁-C₄-alkyl or halogen atoms, inparticular fluorine atoms.

The radical R′ is hydrogen or an organic radical having a molecularweight of up to 20 000, preferably up to 10 000, in particular up to 5000, bound via a carbon atom, oxygen atom or nitrogen atom. The ligandsused according to the present invention are monophosphines,monophosphinites or monophosphinamidites, i.e. the radical R′ does notinclude a phosphorus atom. Possible radicals R′ are, in particular,alkyl, e.g. alkyl having from 1 to 500 carbon atoms, which may beinterrupted by nonadjacent heteroatoms, in particular oxygen atomsand/or nitrogen atoms; cycloalkyl, aryl, aralkyl, alkoxy, cycloalkoxy,aryloxy, aralkyloxy or acyl. Furthermore, R′ may be a polymeric chain,e.g. Z(CHR″CH₂O)_(x)R′″ or Z(CH₂CH₂NR″)_(x)R′″, where Z is a bridgeconsisting of from 0 to 20 atoms of which adjacent atoms may be part ofa saturated or unsaturated, carbocyclic or heterocyclic ring, and R″ andR′″ are each, independently of one another, hydrogen, alkyl, cycloalkyl,aryl, aralkyl or acyl and x is an integer from 1 to 240, preferably from1 to 60. Examples of bridges Z are —CH₂—CH₂—O—, —CH₂—CH₂—N(R″)—,—CH₂—CH₂— and the like.

Preferred ligands have the formula II,

where

X are each, independently of one another, O or NR,

R are each, independently of one another, hydrogen, alkyl, cycloalkyl,haloalkyl, aryl or aralkyl and

R′ is hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, cycloalkoxy,aryloxy, aralkyloxy, alkylamino, di(alkyl)amino, cycloalkylamino,N-cycloalkyl-N-alkylamino, di(cycloalkyl)amino, arylamino,N-aryl-N-alkylamino, di(aryl)amino, aralkylamino,N-aralkyl-N-alkylamino, N-aralkyl-N-arylamino, di(aralkyl)amino, acyl orcarbamoyl.

For the purposes of the present invention, the expressions employed(including those in compound nouns such as alkylamino and the like) havethe following meanings:

“Alkyl”: straight-chain or branched alkyl, preferably C₁-C₂₀-alkyl, inparticular C₁-C₈-alkyl, particularly preferably C₁-C₄-alkyl; examples ofalkyl groups are, in particular, methyl, ethyl, propyl, isopropyl,n-butyl, 2-butyl, s-butyl, t-butyl, n-pentyl, 2-pentyl, 2-methylbutyl,3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl,3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl,3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl;

“Cycloalkyl”: preferably C₅-C₇-cycloalkyl such as cyclopentyl,cyclohexyl or cycloheptyl;

“Haloalkyl”: preferably C₁-C₄-haloalkyl, i.e. a C₁-C₄-alkyl radicalwhich is partially or fully substituted by fluorine, chlorine, bromineand/or iodine, e.g. chloromethyl, dichloromethyl, trichloromethyl,fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl,2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl,2-fluoropropyl, 3-fluoroproipyl, 2,2-difluoropropyl, 2,3-difluoropropyl,2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl,3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl,2,2,3,3,3-pentafluoropropyl, heptafluoropropyl,1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl,1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyland nonafluorobutyl;

“Aryl”: preferably C₆-C₁₆-aryl such as phenyl, tolyl, xylyl, mesityl,naphthyl, anthracenyl, phenanthrenyl, naphthacenyl; in particular phenylor naphthyl;

“Aralkyl”: preferably C₇-C₂₀-aralkyl, in particular phenyl-C₁-C₄-alkylsuch as benzyl or phenethyl;

“Alkoxy”: preferably C₁-C₂₀-alkoxy in which the alkyl group ispreferably as defined above;

“Cycloalkyloxy”: preferably C₅-C₇-cycloalkyloxy in which the cycloalkylgroup is preferably as defined above;

“Aryloxy”: preferably C₇-C₁₆-aryloxy in which the aryl group ispreferably as defined above;

“Aralkyloxy”: preferably C₇-C₂₀-aralkyloxy in which the aralkyl group ispreferably as defined above; and

“Acyl”: preferably C₁-C₂₁-acyl such as formyl or C₁-C₂₀-alkylcarbonyl inwhich the alkyl group is preferably as defined above;

“Carbamoyl”: preferably C₁-C₂₁-carbamoyl such as aminocarbonyl,C₁-C₂₀-alkylaminocarbonyl, C₆-C₁₆-arylaminocarbonyl orC₇-C₂₀-aralkylaminocarbonyl, each preferably having an alkyl, aryl oraralkyl group as defined above.

The radicals X are preferably O, NCH₃ or NH, in particular O.

The radicals R are each, independently of one another, particularlypreferably C₁-C₄-alkyl, C₁-C₄-haloalkyl or phenyl, in particular methyl,t-butyl, trifluoromethyl or phenyl.

Particularly preferred ligands are selected from among

2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane,

2-phenyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane,

2-t-butyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane,

2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decaneand

2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane.

To prepare 6,9,10-trioxa-substituted ligands of the formula I, it ispossible, for example, to react phosphine or a primary phosphine with a1,3-diketone, e.g. 2,4-pentanedione or substituted 2,4-pentanedionessuch as perfluoro-2,4-pentanedione or1,1,1,5,5,5-hexafluoro-2,4-pentanedione, in the presence of an acidcatalyst. The compounds of the formula I are generally obtained in highpurity and can be used directly without further purification. Withregard to suitable reaction conditions, reference may be made to J. Am.Chem. Soc. 1961, Vol. 83, 3279-3282, and Chem. Comm. 1999 (10), 901-902.

In general, the catalysts or catalyst precursors used are convertedunder hydroformylation conditions into catalytically active species ofthe formula H_(x)M_(y)(CO)_(z)L_(q), where M is ruthenium, rhodium,palladium, iridium and/or platinum, L is a ligand of the formula I andq, x, y, z are integers which depend on the valence and type of themetal. The complexes can, if desired, additionally contain furtherligands which are preferably selected from among halides, amines,carboxylates, acetylacetonate, arylsulfonates and alkylsulfonates,olefins, dienes, cycloolefins, nitriles, nitrogen-containingheterocycles, aromatics and heteroaromatics, ethers, PF₃ andmonodentate, bidentate and polydentate phosphine, phosphinite,phosphonite and phosphite ligands which do not correspond to the formulaI.

In a preferred embodiment, the hydroformylation catalysts are preparedin situ in the reactor used for the hydroformylation reaction. However,if desired, the ligand-metal complexes can also be prepared separatelyand isolated by customary methods. For the in situ preparation, it ispossible, for example, to react at least one ligand of the formula I, acompound or a complex of ruthenium, rhodium, palladium, iridium and/orplatinum, optionally at least one further ligand and optionally anactivating agent in an inert solvent with carbon monoxide and hydrogenunder hydroformylation conditions.

Suitable rhodium compounds or complexes are, for example, rhodium(II)and rhodium(III) salts such as rhodium(III) chloride, rhodium(III)nitrate, rhodium(III) sulfate, potassium rhodium sulfate, rhodium(II)and rhodium(III) carboxylates such as rhodium(II) and rhodium(III)acetate, rhodium(III) oxide, salts of rhodic(III) acid,trisammoniumhexachlororhodate(III) etc. Rhodium complexes such asdicarbonylrhodium acetylacetonate, acetylacetonatobisethylenerhodium(I),etc., are also useful. Preference is given to using dicarbonylrhodiumacetylacetonate or rhodium acetate.

Ruthenium salts or compounds are also suitable. Suitable ruthenium saltsare, for example, ruthenium(III) chloride, ruthenium(IV), ruthenium(VI)or ruthenium(VIII) oxide, alkaline metal salts of ruthenium oxo acids,e.g. K₂RuO₄ or KRuO₄, or complexes such as RuHCl(CO)(PPh₃)₃. It is alsopossible to use carbonyls of ruthenium, e.g. dodecacarbonyltrirutheniumor octadecacarbonylhexaruthenium, or mixed forms in which CO has partlybeen replaced by triorganophosphines, e.g. Ru(CO)(PPh₃)₂.

Suitable palladium, iridium and platinum compounds and complexes areknown to those skilled in the art and are adequately described in theliterature. The metal is preferably rhodium.

Suitable activating agents are, for example, Brönsted acids, Lewis acidssuch as BF₃, AlCl₃, ZnCl₂, and Lewis bases.

The molar ratio of ligand of the formula I to metal is generally in arange from about 50:1 to 1:1, preferably from 10:1 to 1:1.

Possible substrates for the process of the present invention are inprinciple all compounds which contain one or more ethylenicallyunsaturated double bonds. These include, for example, olefins such asα-olefins, internal linear and internal branched olefins. Suitableα-olefins are, for example, ethylene, propene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,1-dodecene, etc.

Preferred internal linear olefins are C₄-C₂₀-olefins such as 2-butene,2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene,4-octene, etc.

Preferred internal branched olefins are C₅-C₂₀-olefins such as2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene.

Preferred starting materials are oligo(C₃-C₆-alkenes) orpoly(C₃-C₆-alkenes), which are the oligomerization or polymerizationproducts of C₃-C₆-alkenes such as propene, 1-butene, 2-butene,isobutene, pentene or hexenes. Preferred examples are propene trimer,butene dimer, butene trimer and hexene dimer and also polyisobutenehaving from 20 to 400 carbon atoms. The oligo(C₃-C₆-alkenes), orpoly(C₃-C₆-alkenes) are generally mixtures of essentiallymonounsaturated olefin isomers having a proportion of internal branchedolefins.

Further suitable olefins for the hydroformylation process arevinylaromatics such as styrene, α-methylstyrene, 4-isobutylstyrene, etc.

Further suitable ethylenically unsaturated compounds areα,β-ethylenically unsaturated monocarboxylic and dicarboxylic acids,their esters, monoesters and amides, diacrylic acid, methacrylic acid,maleic acid, fumaric acid, crotonic acid, itaconic acid, methyl3-pentenoate, methyl 4-pentenoate, methyl oleate, alkyl acrylates, alkylmethacrylates, unsaturated nitrites such as 3-pentenenitrile,4-pentenenitrile, acrylonitrile, vinyl ethers such as vinyl methylether, vinyl ethyl ether, vinyl propyl ether, etc.

The process of the present invention is particularly advantageous whenat least one linear compound having an internal double bond, i.e. acompound of the formula III, and/or at least one compound having aninternal branched double bond, i.e. a compound of the formula IV,

where

R^(a) are, independently of one another, radicals different fromhydrogen, in particular alkyl, and

R^(b) is hydrogen or a radical different from hydrogen, in particularalkyl,

is/are used as ethylenically unsaturated compound(s).

The sum of the numbers of carbon atoms in the radicals R^(a) in theformula III is preferably from 2 to 30, in particular from 2 to 12. Thesum of the numbers of carbon atoms of the radicals R^(a) and R^(b) inthe formula IV is preferably from 3 to 30, in particular from 3 to 12.Preferred examples of such compounds are the internal linear andinternal branched olefins mentioned above.

The hydroformylation reaction can be carried out continuously,semicontinuously or batchwise. Suitable reactors are known to thoseskilled in the art and are described, for example, in UllmannsEnzyklopädie der Technischen Chemie, Volume 1, 3^(rd) edition, 1951, p.743ff.

Carbon monoxide and hydrogen are customarily used in the form of amixture, known as synthesis gas. The molar ratio of carbon monoxide tohydrogen is generally from about 5:95 to 70:30, preferably from about40:60 to 60:40. In particular, a molar ratio of carbon monoxide tohydrogen in the region of about 1:1 is used.

The temperature in the hydroformylation reaction is generally in a rangefrom about 80 to 180° C., preferably from about 100 to 160° C. Thereaction is generally carried out at the partial pressure of thereaction gas at the reaction temperature chosen. In general, thepressure is in a range from about 10 to 100 bar, in particular from 10to 80 bar. The optimum temperature and the optimum pressure depend onthe ethylenically unsaturated compound used. Thus, α-olefins areparticularly preferably hydroformylated at from 80 to 120° C. and apressure of from 10 to 40 bar. Internal and internal branched olefinsare preferably hydroformylated at from 120 to 180° C. and a pressure offrom 2 to 80 bar, with internal linear olefins being particularlypreferably reacted at from 2 to 20 bar and internal branched olefinsbeing particularly preferably reacted at from 40 to 80 bar.

The catalytically active ligand-metal complexes can be separated fromthe product mixture from the hydroformylation reaction by customarymethods known to those skilled in the art and can generally, ifnecessary after work-up, be reused for the hydroformylation.

The hydroformylation can be carried out using solvents such as thehigh-boiling subsequent reaction products of the aldehydes which areformed in the hydroformylation. Suitable solvents likewise includearomatic hydrocarbons such as toluene and xylene, aliphatichydrocarbons, ethers such as 2,5,8-trioxanonane (diglyme), diethyl etherand anisole, sulfones, such as sulfolane, or esters such as3-hydroxy-2,2,4-trimethylpentyl 1-isobutyrate (Texanol).

The invention is illustrated by the following nonlimiting examples.

EXAMPLES

The ligands were synthesized in a manner analogous to the preparativemethod described in J. Am. Chem. Soc. 1961, Vol. 83, 3279+3282 and Chem.Colum. 1999 (10) 901-902. The butene dimer used in the examples wasobtained by dimerization of a 1-butene- and 2-butene-containingC₄-hydrocarbon mixture over a heterogeneous, nickel-containing catalyst.It contained about 20% by weight of internal branched olefins. Theabbreviation “acac” represents acetylacetonate; “L:M” is the molar ratioof ligand to metal.

Example 1

Hydroformylation of 1-octene using2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

0.9 mg of Rh(CO)₂acac and 52 mg of

2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane (60 ppm of Rh, L:M=50:1) were weighed into areaction vessel, dissolved in 3 g of toluene and treated at 100° C. with10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactor wasdepressurized, 3 g of 1-octene were then added and the mixture washydroformylated at 100° C. and 10 bar for 4 hours. The conversion was98%, and the aldehyde selectivity was 99%.

Example 2

Hydroformylation of butene dimer using2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of Rh(CO)₂acac and 32 mg of

2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane (60 ppm of Rh, L:M=10:1) were weighed into areaction vessel, dissolved in 10 g of toluene and treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 160° C. and 60 bar for 4 hours. The conversionwas 94%, the nonanal selectivity was 99% and the nonanol selectivity was1%.

Example 3

Hydroformylation of butene dimer using2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of Rh(CO)₂acac and 35 mg of

2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane (60 ppm of Rh, L:M=10:1) were weighed into areaction vessel, dissolved in 10 g of toluene and treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 140° C. and 60 bar for 4 hours. The conversionwas 94%, the nonanal selectivity was 99% and the nonanol selectivity was1%.

Example 4

Hydroformylation of 1-octene using2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of Rh(CO)₂acac and 125.6 mg of

2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}] decane(60 ppm of Rh, L:M=50:1) were dissolved separately in a total of 10 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of 1-octene were then added and the mixture washydroformylated at 100° C. and 10 bar for 4 hours. The conversion was29%, and the aldehyde selectivity was 100%.

Example 5

Hydroformylation of butene dimer using2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of Rh(CO)₂acac and 25.1 mg of

2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}] decane(60 ppm of Rh, L:M=10:1) were dissolved separately in a total of 10 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 160° C. and 80 bar for 4 hours. The conversionwas 88%, the nonanal selectivity was 89% and the nonanol selectivity was2%.

Example 6

Hydroformylation of 1-octene using2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

0.75 mg of Rh(CO)₂acac and 28.6 mg of

2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane(60 ppm, L:M=30:1) were dissolved separately in a total of 2.5 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 2.5 g of 1-octene were then added and the mixture washydroformylated at 100° C. and 10 bar for 4 hours. The conversion was98%, the aldehyde selectivity was 100% and the linearity was 56%.

Example 7

Hydroformylation of butene dimer using2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of Rh(CO)₂acac and 6.9 mg of

2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane (60 ppm of Rh, L:M=2:1) were dissolved separatelyin a total of 10 g of toluene, the solutions were mixed and the mixturewas treated at 100° C. with 10 bar of synthesis gas (CO:H₂=1:1). After30 minutes, the reactor was depressurized, 10 g of butene dimer werethen added and the mixture was hydroformylated at 140° C. and 60 bar for4 hours. The conversion was 74%, and the nonanal selectivity was 100%.

Example 8

Hydroformylation of butene dimer using2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of RH(CO)₂acac and 38.1 mg of

2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane(60 ppm of Rh, L:M=10:1) were dissolved separately in a total of 10 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 140° C. and 40 bar for 4 hours. The conversionwas 48%, and the nonanal selectivity was 100%.

Example 9

Hydroformylation of butene dimer using2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of RH(CO)₂acac and 38.1 mg of

2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane(60 ppm of Rh, L:M=10:1) were dissolved separately in a total of 10 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 140° C. and 60 bar for 4 hours. The conversionwas 74%, the nonanal selectivity was 99% and the nonanol selectivity was1%.

Example 10

Hydroformylation of butene dimer using2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of RH(CO)₂acac and 38.1 mg of

2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane(60 ppm of Rh, L:M=10:1) were dissolved separately in a total of 10 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 140° C. and 80 bar for 4 hours. The conversionwas 88%, the nonanal selectivity was 99% and the nonanol selectivity was1%.

Example 11

Hydroformylation of butene dimer using2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

2 mg of RH(CO)₂acac and 38.1 mg of

2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane(60 ppm of Rh, L:M=10:1) were dissolved separately in a total of 10 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 160° C. and 40 bar for 4 hours. The conversionwas 44%, the nonanal selectivity was 98% and the nonanol selectivity was2%.

Example 12

Hydroformylation of butene dimer using2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of RH(CO)₂acac and 38.1 mg of

2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane(60 ppm of Rh, L:M=10:1) were dissolved separately in a total of 10 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 160° C. and 60 bar for 4 hours. The conversionwas 72%, the nonanal selectivity was 94%, the nonanol selectivity was 3%and the proportion of aldol was 3%.

Example 13

Hydroformylation of butene dimer using2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane

3 mg of RH(CO)₂acac and 38.1 mg of

2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane(60 ppm of Rh, L:M=10:1) were dissolved separately in a total of 10 g oftoluene, the solutions were mixed and the mixture was treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 160° C. and 80 bar for 4 hours. The conversionwas 83%, the nonanal selectivity was 89%, the nonanol selectivity was 5%and the proportion of aldol was 6%.

Comparative Example A

Hydroformylation of butene dimer using1,3-P,P′-di(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decyl)-propane

3 mg of Rh(CO)₂acac and 274 mg of

1,3-P,P′-di(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decyl)propane (60 ppm of Rh, L:M=50:1) were weighed into areaction vessel, dissolved in 10 g of toluene and treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of butene dimer were then added and the mixturewas hydroformylated at 160° C. and 80 bar for 4 hours. The conversionwas 2%, and the nonanal selectivity was 100%.

Comparative Example B

Hydroformylation of butene dimer using1,3-P,P′-di(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decyl)propane

Comparative example A was repeated using an L:M of 10:1. This gave thesame result as comparative example A.

Comparative Example C

Hydroformylation of 2-octene using1,3-P,P′-di(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decyl)propane

3 mg of Rh(CO)₂acac and 274 mg of

1,3-P,P′-di(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decyl)propane (60 ppm of Rh, L:M=50:1) were weighed into areaction vessel, dissolved in 10 g of toluene and treated at 100° C.with 10 bar of synthesis gas (CO:H₂=1:1). After 30 minutes, the reactorwas depressurized, 10 g of 2-octene were then added and the mixture washydroformylated at 160° C. and 80 bar for 4 hours. The conversion was14%, and the aldehyde selectivity was 79%.

Comparative example D

Hydroformylation of butene dimer using triphenylphosphine

7.5 g of Rh(CO)₂acac and 157 mg of triphenylphosphine (60 ppm of Rh,L:M=20:1) were dissolved separately in a total of 25 g of toluene, thesolutions were mixed and the mixture was treated at 100° C. with 10 barof synthesis gas (CO:H₂=1:1). After 30 minutes, the reactor wasdepressurized, 25.1 g of butene dimer were then added and the mixturewas hydroformylated at 160° C. and 60 bar for 4 hours. The conversionwas 9%, and the nonanal selectivity was 47%.

I claim:
 1. A process for the hydroformylation of ethylenicallyunsaturated compounds, in which at least one ethylenically unsaturatedcompound is reacted with carbon monoxide and hydrogen in the presence ofa ligand-metal complex of ruthenium, rhodium, palladium, iridium and/orplatinum, where the ligand-metal complex comprises a monophosphine,monophosphinite or monophosphineamidite wherein the ligand has theformula II

 where X are each, independently of one another O or NR, R are each,independently of one another, hydrogen, alkyl, cycloalkyl, haloalkyl,aryl or aralkyl and R′ is hydrogen, alkyl, cycloalkyl, aryl, aralkyl,alkoxy, cycloalkoxy, aryloxy, aralkyloxy, alkylamino, di(alkyl)amino,cycloalkylamino, N-cycloalkyl-N-alkylamino, di(cycloalkyl) amino,arylamino, N-aryl-N-alkylamino, di(aryl)amino, aralkylamino,N-aralkyl-N-alkylamino, N-aralkyl-N-arylamino, di(aralkyl)amino, acyl orcarbamoyl.
 2. A process as claimed in claim 1, wherein the radicals Rare each, independently of one another, methyl, t-butyl, trifluoromethylor phenyl.
 3. A process as claimed in claim 2, wherein the ligand isselected from among2-cyclohexyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}decane,2-octyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane,2-phenyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane,2-t-butyl-2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane 2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}]decane.
 4. A process as claimed in claim 1, wherein at least onecompound of the formula III or IV,

where R^(a) are, independently of one another, radicals different fromhydrogen and R^(b) is hydrogen or a radical different from hydrogen, isused as ethylenically unsaturated compound.
 5. A process as claimed inclaim 4, wherein an oligo(C₃-C₅-alkene) or poly(C₃-C₆-alkene) is used asethylenically unsaturated compound.
 6. A ligand-metal complex comprisinga metal selected from among ruthenium, rhodium, palladium, iridiumand/or platinum and at least one monophosphine, monophosphinite ormonophosphinamidite wherein the ligand has the formula II

 where X are each, independently of one another O or NR, R are each,independently of one another, hydrogen, alkyl, cycloalkyl, haloalkyl,aryl or aralkyl and R′ is hydrogen, alkyl, cycloalkyl, aryl, aralkyl,alkoxy, cycloalkoxy, aryloxy, aralkyloxy, alkylamino, di(alkyl)amino,cycloalkylamino, N-cycloalkyl-N alkylamino, di(cycloalkyl) amino,arylamino, N-aryl-N-alkylamino, di(aryl)amino, aralkylamino,N-aralkyl-N-alkylamino, N-aralkyl-N-arylamino, di(aralkyl)amino, acyl orcarbamoyl.